Graphene quantum dots (GQDs) are nanoparticles that consist of a nanometer-sized core of graphene with diverse chemical groups on its boundary. Due to their advantageous properties, they are considered to be a promising material for optoelectronics, bioimaging, or photovoltaics. Despite considerable efforts that have been focused on unraveling the mechanism of their photoluminescence, many fundamental details are still unclear. Here, we report on a single-particle multimodal study that provides new insight into the photoluminescence properties of emission centers of GQDs in various local chemical environments. In particular, we show that the properties that are associated with emission centers of GQDs are significantly more sensitive to the structure of the particle itself than to a nonuniform local chemical environment. A better understanding of the dependence of GQDs' emission states on the complex local chemical environment is an important step toward finding new ways of controlling the optical properties of GQDs and of optimizing their use in various applications.